WO1998046661A1 - Process for the preparation of antimony ethylene glycolate - Google Patents
Process for the preparation of antimony ethylene glycolate Download PDFInfo
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- WO1998046661A1 WO1998046661A1 PCT/JP1997/003432 JP9703432W WO9846661A1 WO 1998046661 A1 WO1998046661 A1 WO 1998046661A1 JP 9703432 W JP9703432 W JP 9703432W WO 9846661 A1 WO9846661 A1 WO 9846661A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
- C07F9/902—Compounds without antimony-carbon linkages
Definitions
- the present invention relates to a method for producing a polyester resin such as polyethylene terephthalate, which is used for producing a polyester resin by a reaction.
- antimony compounds are known as polycondensation of polyester resins. Typical examples are antimony trioxide, antimony acetate, antimony ethylene glycolate, antimony ethylene dalioxide, trisalt antimony and the like.
- Antimony trioxide is inexpensive but somewhat poorly active, and antimony acetate is more reactive than antimony trioxide, resulting in a smaller amount of metal antimony conversion, but on the other hand expensive. It also has the disadvantage that it reacts with moisture in the air to convert acetic acid into ⁇ ⁇ and easily changes to antimony oxyacetate.
- antimony ethylene glycolate and antimony ethylene dalioxide which are SJiT of antimony and ethylene glycol, are very effective, but their methods for producing them at low cost were not known. I have not.
- Japanese Patent Publication No. 57-35840 proposes a method for producing antimony ethylene glyoxide by reacting antimony tris organic carboxylate with at least 1.5 equivalents of ethylene glycol. However, according to this method, it is presumed that the antimony tris organic carboxylate is easily converted to antimony ethylene glycolate or antimony ethylene glyoxide under the conditions of the combined reaction. There is no. Also, using antimony tris organic carboxylate as raw material
- An object of the present invention is to provide a method for inexpensively producing antimony ethylene glyoxide having excellent performance from antimony and ethylene glycol. Disclosure of the invention
- the present invention proposes a method for producing antimony ethylene glyoxide by reacting antimony halide with ethylene glycol as a means for solving the above-mentioned problems.
- the antimony halide used in the present invention is antimony trichloride, antimony tribromide, antimony triiodide, antimony trifluoride, antimony pentachloride, antimony pentabromide, antimony pentaioride, pentafluoride.
- Compounds of antimony, such as antimony halide, with a halogen group can be used. These, especially antimony trichloride and antimony tribromide, are commercially sold by directly reacting metal antimony with halogen.
- the antimony halide is subjected to a direct dehydrogenation reaction with ethylene glycol to give antimony ethylene glyoxide. At that time, it is desirable to shut off moisture in the air with an inert gas. It is desirable that the blending amount of ethylene glycol be equal to or more than the molar equivalent of antimony halide.
- This nitrogen-containing organic compound is a nitrogen-containing organic compound containing ammonia having an ability to form an amidium salt as a by-product hydrogen halide when reacting the above-mentioned antimony halide with ethylene glycol.
- Specific examples include various amine compounds and ammonia. More specifically, compounds represented by the following formula 1 (wherein, in the formula 1, R 2 and R 3 each have 1 to 1 carbon atoms) One of aliphatic hydrocarbons, hydrogen, and aromatic carbons having 8), bicyclic nitrogen-containing compounds, diamine compounds, and ammonia.
- examples thereof include n-octylamine, aniline, N-methylaniline, diphenylamine, and triphenylamine.
- the heterocyclic nitrogen-containing compound include pyridine, piperidine, N-methylpyridine and the like, and examples of the diamine compound include ethylenediamine and hexamethylenediamine.
- Example 1 45.6 g of antimony chloride was added to 341 g of ethylene glycol, and the mixture was stirred at about 40 ° C and stirred to obtain a uniform mixture. To this solution was added a solution consisting of 60.8 g of triethylamine and 186 g of ethylene glycol. At the same time, the temperature was _h and the white precipitate was ⁇ . The reaction mixture was placed, filtered and evacuated to obtain 31.6 g of antimony ethylene glyoxide. The antimony content of this product was measured and found to be 57.26%. (Theoretical antimony content: 57.49%)
- Example III 22.8 g of antimony Sanshidani was added to 5.5 g of ethylene glycol, and the mixture was heated and stirred at about 40 ° C to obtain a uniform dish. To this was added 21.9 g of getylamine and 93 g of ethylene glycol, and the mixture was mixed. At the same time, the temperature rose and a white precipitate was formed. The reaction mixture was allowed to stand overnight, dried in vacuo, and 16.7 g of antimony ethylene glyoxide was obtained. The antimony content of this product was measured and found to be 57.25%.
- Example 6 45.8 g of Sanshiri-dani antimony was dissolved in 124 g of ethylene glycol, and 60.6 g of triethylamine was further added. The liquid temperature rose by 80 to 90 ° C, a white precipitate formed immediately after mixing, and crystals formed ⁇ after 1 to 2 hours. The precipitate was antimony ethylene glyoxide, and the crystals could be triethylamine hydrochloride.
- ethylene glycol sufficient to dissolve all the by-product amidium salts of halogenated bTK is coexisted.
- Comparative Example 1 As a comparative example with respect to the above example, 59.8 g of antimony acetate, 31 g of ethylene glycol and 200 ml of orthoxylene were reacted at 145 ° C. for 20 hours. Was. The by-produced acetic acid was removed, and the solid content was suctioned off, washed with orthoxylene, and dried at 90 ° C. for 3 hours to obtain 27 g of a white powder. The antimony ⁇ M of this product was measured and found to be 80.5%. The target antimony ethylene glyoxide was scarcely obtained, and antimony trioxide was formed.
- the first invention of the present application is an antimony useful as a polycondensation of a polyester resin by reacting an antimony halide with ethylene glycol.
- Ethylene glyoxide can be produced at low cost.
- the above-mentioned H reaction can proceed smoothly by allowing the above-mentioned nitrogen-containing organic compound containing ammonia to coexist in the reaction system.
- the third invention by adding an equimolar amount of an antimony halide to the nitrogen-containing organic compound, only the target antimony ethylene glyoxide can be reduced, and the purification process is unnecessary. Was able to do so.
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- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
明 細 書 アンチモンエチレンダリオキサイドの製造方法 技術分野 Description Manufacturing method of antimony ethylene dalioxide Technical field
本 ®¾明は、 ポリエチレンテレフタレートなどのポリエステル樹脂を 合反 応により製造する際に使用される,の製造方法に関するものである。 背景技術 The present invention relates to a method for producing a polyester resin such as polyethylene terephthalate, which is used for producing a polyester resin by a reaction. Background art
ポリエステル樹脂の重縮合 として、 種々のァンチモン化合物が知られてい る。 その代表的なものは、三酸化アンチモン、酢酸アンチモン、 アンチモンェチ レングリコレート、 アンチモンエチレンダリオキサイド、 三塩[匕アンチモンなど である。 Various antimony compounds are known as polycondensation of polyester resins. Typical examples are antimony trioxide, antimony acetate, antimony ethylene glycolate, antimony ethylene dalioxide, trisalt antimony and the like.
三酸化アンチモンは、安価であるが、 やや 性に乏しく、酢酸アンチモンは 三酸化ァンチモンに比べて、反応性に優れその結果として金属ァンチモン換算で の添加量が少なくすむが、 その一方高価であり、 また空気中の水分と反応して酢 酸を ¾ ^し、 ォキシ酢酸アンチモンに変質しやすいという欠点がある。 Antimony trioxide is inexpensive but somewhat poorly active, and antimony acetate is more reactive than antimony trioxide, resulting in a smaller amount of metal antimony conversion, but on the other hand expensive. It also has the disadvantage that it reacts with moisture in the air to convert acetic acid into 変 ^ and easily changes to antimony oxyacetate.
また、 アンチモンとエチレングリコールの SJiT、^^物である、 アンチモンェチ レングリコレートやアンチモンエチレンダリオキサイドは、 きわめて有効な , であるが、安価に製造する方法が知られていなかつたため、広く使われるにいた つていない。 特公昭 57— 35840では、 アンチモンエチレングリオキサイドを製造 する方法として、 アンチモントリス有機カルボキシレートを少なくとも 1. 5当 量のエチレングリコールと反応させる方法が提案されている。 しかしながらこの 方法では、 アンチモントリス有機カルボキシレートは 合反応条件下で、容易 にアンチモンエチレングリコレート又はアンチモンエチレングリオキサイドに変 化しているものと推定され、 わざわざ事 ijにアンチモンエチレングリオキサイド を製造する意味が無い。 またアンチモントリス有機カルボキシレートを原料とし Also, antimony ethylene glycolate and antimony ethylene dalioxide, which are SJiT of antimony and ethylene glycol, are very effective, but their methods for producing them at low cost were not known. I have not. Japanese Patent Publication No. 57-35840 proposes a method for producing antimony ethylene glyoxide by reacting antimony tris organic carboxylate with at least 1.5 equivalents of ethylene glycol. However, according to this method, it is presumed that the antimony tris organic carboxylate is easily converted to antimony ethylene glycolate or antimony ethylene glyoxide under the conditions of the combined reaction. There is no. Also, using antimony tris organic carboxylate as raw material
1 1
差替 え 用紙 （規則 26) ているため、 コス卜的にアンチモントリス有機カルボキシレ一卜に劣ることは明 らかである。 Replacement form (Rule 26) Therefore, it is clear that the cost is inferior to antimony tris organic carboxylates.
本,明の課題は、 アンチモンとエチレングリコ一ルから、優れた 性能を 有するアンチモンエチレングリオキサイドを、安価に製造する方法を提供するこ とにある。 発明の開示 An object of the present invention is to provide a method for inexpensively producing antimony ethylene glyoxide having excellent performance from antimony and ethylene glycol. Disclosure of the invention
本,明は、上記の課題の解決手段として、 ハロゲン化アンチモンとエチレン グリコールを反応させ、 アンチモンエチレングリオキサイドを製造する方法を提 案するものである。 The present invention proposes a method for producing antimony ethylene glyoxide by reacting antimony halide with ethylene glycol as a means for solving the above-mentioned problems.
本 K¾明に用いられるハロゲン化アンチモンは、三塩ィ匕アンチモン、 三臭化ァ ンチモン、 三沃化アンチモン、三フッ化アンチモン、 五塩化アンチモン、五臭化 アンチモン、五沃ィ匕アンチモン、五フッ化アンチモン等々のアンチモンとハロゲ ン族との化 ^を用いることができる。 これら、特に三塩化アンチモン、三臭化 アンチモン等は、 金属アンチモンとハロゲンを直接反応させることにより、 工業 的に 販売されている。 The antimony halide used in the present invention is antimony trichloride, antimony tribromide, antimony triiodide, antimony trifluoride, antimony pentachloride, antimony pentabromide, antimony pentaioride, pentafluoride. Compounds of antimony, such as antimony halide, with a halogen group can be used. These, especially antimony trichloride and antimony tribromide, are commercially sold by directly reacting metal antimony with halogen.
このハロゲン化ァンチモンをェチレングリコールと直接脱/ヽ口ゲン化水素反応 せしめ、 アンチモンエチレングリオキサイドを得る。 その際、 不活性ガスで、 空 気中の水分を遮断することが望ましい。 エチレングリコールの配合量は、 ハロゲ ン化アンチモンと等量モル以上とすることが望ましい。 The antimony halide is subjected to a direct dehydrogenation reaction with ethylene glycol to give antimony ethylene glyoxide. At that time, it is desirable to shut off moisture in the air with an inert gas. It is desirable that the blending amount of ethylene glycol be equal to or more than the molar equivalent of antimony halide.
また、 上記ハロゲン化アンチモンとエチレングリコールとの反応を円滑に進行 させるためは、 副生するハロゲン化水素と反応し、 アミ二ゥム塩を生 J¾する能力 を有するァミン化^！等の含窒素有機化合物を、 ハロゲン化アンチモンの等量モ ル以上添加することが望ましい。 アミニゥム塩の^^応は、発^ 応であるた め、必 に応じて反応1を冷却し、 または、含窒素有機化合物を予めエチレング リコ一ルに溶解し、結果的に多量のェチレングリコ一ルを介在させることにより 、発熱温度を調整することができる。 In addition, in order to allow the reaction between the antimony halide and ethylene glycol to proceed smoothly, an amination having the ability to react with the by-produced hydrogen halide to produce an ammonium salt! It is desirable to add a nitrogen-containing organic compound such as the above in an equivalent amount of antimony halide. Since the reaction of an aluminum salt is a reaction, the reaction 1 is cooled if necessary, or a nitrogen-containing organic compound is dissolved in ethylene glycol in advance, resulting in a large amount of ethylene glycol. The intervening makes it possible to adjust the heat generation temperature.
2 Two
差替え用紙 （規則 26) この含窒素有機化合物は、上記のハロゲン化アンチモンとエチレングリコール を反応させるに際して、 副生するハロゲン化水素と し、 アミ二ゥム塩を^^ する能力を有するアンモニアを含む含窒素有機化合物であり、具体的には、種々 のァミン化合物やアンモニアを挙げることができ、 より詳しくは、 下記の式 1に 示される化合物 （但し、 式 1において、 、 R2、 R3 は、 炭素数 1〜1 8を 持つ脂脑炭化水素、水素、 芳香族炭 素の 1つ） や、観環式含窒素化合物 、 ジァミン化合物、 アンモニア等を挙げることができる。 より具体的には、 式 1 に示されるィ匕合物として、 メチルァミン、 ェチルァミン、 プロピルァミン、 n— ォクチルァミン、 ジメチルァミン、 ジェチルァミン、 ジプロピルァミン、 ジー n —ォクチルァミン、 トリメチルァミン、 トリェチルァミン、 トリプロピルアミン 、 トリ一 n—ォクチルァミン、 ァニリン、 N—メチルァニリン、 ジフエニルアミ ン、 トリフヱニルァミン等を例示し得る。 複素環式含窒素化合物としては、 ピリ ジン、 ピぺリジン、 N—メチルピリジン等、 ジァミン化合物としては、 エチレン ジァミン、 へキサメチレンジァミン等を例示し得る。 Replacement form (Rule 26) This nitrogen-containing organic compound is a nitrogen-containing organic compound containing ammonia having an ability to form an amidium salt as a by-product hydrogen halide when reacting the above-mentioned antimony halide with ethylene glycol. Specific examples include various amine compounds and ammonia. More specifically, compounds represented by the following formula 1 (wherein, in the formula 1, R 2 and R 3 each have 1 to 1 carbon atoms) One of aliphatic hydrocarbons, hydrogen, and aromatic carbons having 8), bicyclic nitrogen-containing compounds, diamine compounds, and ammonia. More specifically, as the conjugate represented by the formula 1, methylamine, ethylamine, propylamine, n-octylamine, dimethylamine, getylamine, dipropylamine, g-n-octylamine, trimethylamine, triethylamine, tripropylamine, tripropylamine Examples thereof include n-octylamine, aniline, N-methylaniline, diphenylamine, and triphenylamine. Examples of the heterocyclic nitrogen-containing compound include pyridine, piperidine, N-methylpyridine and the like, and examples of the diamine compound include ethylenediamine and hexamethylenediamine.
〔式 1〕
N
このように、 ハロゲン化アンチモン、 エチレングリコールに加えて、 上記の含 窒素有機化合物を反応させるに際しては、 副生するすべてのハロゲン化水素のァ ミ二ゥム塩を溶解するに足りるエチレングリコ一ルを共存させることが望ましく As described above, when reacting the above-mentioned nitrogen-containing organic compound in addition to the antimony halide and ethylene glycol, ethylene glycol which is sufficient to dissolve all the by-product amide salts of hydrogen halide is dissolved. It is desirable to coexist
3 Three
差替 え 用紙 （規則 26) W Replacement form (Rule 26) W
、 これによつて、 目的のアンチモンエチレングリオキサイドのみを容易に^す ることができるものである。 発明を実施するための最良の形態 Thus, only the desired antimony ethylene glyoxide can be easily obtained. BEST MODE FOR CARRYING OUT THE INVENTION
以下、 本願発明の理解を高めるために、 その実施例を示すが、 本願発明はこの 実施例に限定して されるべきではない。 Hereinafter, in order to enhance the understanding of the present invention, examples thereof will be described. However, the present invention should not be limited to these examples.
〔¾½例 1〕 4 5. 6 gの-塩化アンチモンを 3 4 1 gのエチレングリコールに 添加し、 約 4 0 ° Cの で加^ M拌し、 均—な を得た。 この溶液に 6 0. 8 gのトリエチルアミンと 1 8 6 gのエチレングリコールからなる溶液を添加し た。 両者が混合されると同時に液温が _h し白色沈殿が^^した。 反応混合物を 一 置し、濾過、真空 しアンチモンエチレングリオキサイド 3 1 . 6 gを 得た。 このもののアンチモン含量を測定したところ、 5 7. 2 6 %であった。 （ アンチモンの理論含有量： 5 7. 4 9 %) [Example 1] 45.6 g of antimony chloride was added to 341 g of ethylene glycol, and the mixture was stirred at about 40 ° C and stirred to obtain a uniform mixture. To this solution was added a solution consisting of 60.8 g of triethylamine and 186 g of ethylene glycol. At the same time, the temperature was _h and the white precipitate was ^^. The reaction mixture was placed, filtered and evacuated to obtain 31.6 g of antimony ethylene glyoxide. The antimony content of this product was measured and found to be 57.26%. (Theoretical antimony content: 57.49%)
mm 2) 反応温度を 9 0 ° Cに保った以外は、実施例 1と同一の条件で反 応させ、 アンチモン含量 5 7. 1 2 %のアンチモンエチレングリオキサイド 2 9 . 6 gを得た。 mm 2) The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was kept at 90 ° C., to obtain 29.6 g of antimony ethylene glyoxide having an antimony content of 57.2%.
〔H¾例 3〕 2 2. 8 gの三塩ィ匕アンチモンを 1 5 5 gのエチレングリコール に添加し、 約 4 0 ° Cの で加熱攪拌し、均一な皿を得た。 この に 2 1 . 9 gのジェチルァミンと 9 3 gのエチレングリコールからなる^ ¾を添加した o 両者が混合されると同時に液温が上昇し白色沈殿が生成した。 反応混合物を一 夜放置し、 Μ、真空乾燥しアンチモンエチレングリオキサイド 1 6. 7 gを得 た。 このもののアンチモン含量を測定したところ 5 7. 2 5 %であった。 [Example III] 22.8 g of antimony Sanshidani was added to 5.5 g of ethylene glycol, and the mixture was heated and stirred at about 40 ° C to obtain a uniform dish. To this was added 21.9 g of getylamine and 93 g of ethylene glycol, and the mixture was mixed. At the same time, the temperature rose and a white precipitate was formed. The reaction mixture was allowed to stand overnight, dried in vacuo, and 16.7 g of antimony ethylene glyoxide was obtained. The antimony content of this product was measured and found to be 57.25%.
〔HJ¾例 4〕 2 2. 8 gの三塩化アンチモンを 1 5 5 gのエチレングリコール に添加し、 約 4 0 ° Cの- で加 拌し、均—な猶を得た。 この に 2 3 . 7 gのピリジンと 9 3 gのエチレングリコールからなる皿を添加した。 両者 が混合されると同時に液温が上昇し白色沈殿が^^した。 反応混合物を一夜放置 し、 ϋ、 真空乾燥しアンチモンエチレングリオキサイド 1 5. 4 gを得た。 こ [HJ Example 4] 22.8 g of antimony trichloride was added to 1555 g of ethylene glycol, and the mixture was stirred at about 40 ° C to obtain a uniform balance. To this was added a dish consisting of 23.7 g of pyridine and 93 g of ethylene glycol. At the same time as the two were mixed, the temperature rose and a white precipitate formed. The reaction mixture was allowed to stand overnight, dried under reduced pressure, and dried to obtain 15.4 g of antimony ethylene glyoxide. This
4 Four
差替え用紙 （規則 26) W Replacement form (Rule 26) W
のもののアンチモン含量を測定したところ、 5 7. 8 2 %であった。 When the antimony content of the product was measured, it was 57.82%.
〔¾5¾例 5〕 3 6. 1 gの三臭化アンチモンを 1 5 5 gのエチレングリコール に添加し、約 4 0 ° Cの'^で加熱攪拌し、均一な鎌を得た。 この赚に 3 0 . 4 gのトリエチルアミンと 9 3 gのエチレンダリコールからなる;^を添加し た。 両者が混合されると同時に液温が上昇し白色沈^^^^した。 反応混合物を 一夜放置し、 濾過、 真空乾燥しアンチモンエチレングリオキサイド 1 4. 7 gを 得た。 このもののアンチモン含量を測定したところ、 5 7. 7 4 %であった。 [{5} Example 5] 36.1 g of antimony tribromide was added to 150 g of ethylene glycol, and heated and stirred at about 40 ° C to obtain a uniform sickle. To this was added 30.4 g of triethylamine and 93 g of ethylenedalicol; ^ was added. At the same time as the two were mixed, the liquid temperature rose and a white precipitate was formed. The reaction mixture was allowed to stand overnight, filtered, and dried under vacuum to obtain 14.7 g of antimony ethylene glyoxide. The antimony content of the product was measured and found to be 57.74%.
〔¾¾例 6〕 4 5. 8 gの三塩ィ匕アンチモンを 1 2 4 gのエチレングリコール に溶解し、 さらに 6 0. 6 gのトリエチルァミンを添加した。 液温は 8 0〜 9 0 ° C上昇し、混合直後に白色沈澱が するとともに、 1〜2時間後に、結晶が ^^した。 沈澱は、 アンチモンエチレングリオキサイドであり、結晶はトリェチ ルァミンの塩酸塩であることが ¾ できた。 先の実施例 1〜5では、 ハロゲン化 アンチモン、 エチレングリコール、含窒素有機化合物を反応させるに際して、 副 生するすべてのハロゲンィ bTK素のアミ二ゥム塩を溶解するに足りるエチレングリ コールを共存させたため、 アンチモンエチレングリオキサイドのみか された が、 この実施例では、 エチレングリコールの配合量カ沙なく、副生するすべての ハロゲンィ 素のアミ二ゥム塩を溶解するに足りないものであったため、 トリエ チルァミンの塩酸塩の結晶も^^し、 これとの分離精製が必 となる。 [Example 6] 45.8 g of Sanshiri-dani antimony was dissolved in 124 g of ethylene glycol, and 60.6 g of triethylamine was further added. The liquid temperature rose by 80 to 90 ° C, a white precipitate formed immediately after mixing, and crystals formed ^^ after 1 to 2 hours. The precipitate was antimony ethylene glyoxide, and the crystals could be triethylamine hydrochloride. In the above Examples 1 to 5, in reacting antimony halide, ethylene glycol, and a nitrogen-containing organic compound, ethylene glycol sufficient to dissolve all the by-product amidium salts of halogenated bTK is coexisted. Therefore, only antimony ethylene glyoxide was used.However, in this example, the amount of ethylene glycol was not sufficient, and it was insufficient to dissolve all of the by-product amidium salt of halogen. Crystals of triethylamine hydrochloride also form ^^, which must be separated and purified.
〔比較例 1〕 上記実施例に対する比較例として、 5 9. 8 gの酢酸アンチモン と 3 1 gのエチレングリコール及び 2 0 0 m 1のオルソキシレンを、 1 4 5 ° C で 2 0時間反応させた。 副生した酢酸を除去、 した固形分を吸引 ΐ¾ϋし、 ォ ルッキシレンで洗浄後、 9 0 ° Cで 3時間乾燥し、 白色粉末 2 7 gを得た。 この もののアンチモン^ Mを測定したところ、 8 0. 5 %であり、 目的とするアンチ モンエチレングリオキサイドは、 ほとんど得られず、三酸化アンチモンが生成し o Comparative Example 1 As a comparative example with respect to the above example, 59.8 g of antimony acetate, 31 g of ethylene glycol and 200 ml of orthoxylene were reacted at 145 ° C. for 20 hours. Was. The by-produced acetic acid was removed, and the solid content was suctioned off, washed with orthoxylene, and dried at 90 ° C. for 3 hours to obtain 27 g of a white powder. The antimony ^ M of this product was measured and found to be 80.5%. The target antimony ethylene glyoxide was scarcely obtained, and antimony trioxide was formed.
本願の第 1の発明は、 ハロゲン化アンチモンとエチレングリコールとの反応を させることによって、 ポリエステル樹脂の重縮合■として有用な、 アンチモン The first invention of the present application is an antimony useful as a polycondensation of a polyester resin by reacting an antimony halide with ethylene glycol.
5 Five
差替え用紙 （規則 26) エチレングリオキサイドを安価に製造することができたものである。 特に、本願 の第 2の発明においては、特定の上記のァンモニァを含む含窒素有機化合物を反 応系に共存させることによって、上言 H 応を円滑に進行させることができ、 さら に、 本願の第 3の発明にあっては、 含窒素有機化合物を、 ハロゲン化アンチモン の等量モル 添加することによって、 目的とするアンチモンエチレングリオキ サイドのみを^^することができ、精 ¾ 程を不要とすることができたものであ る。 Replacement form (Rule 26) Ethylene glyoxide can be produced at low cost. In particular, in the second invention of the present application, the above-mentioned H reaction can proceed smoothly by allowing the above-mentioned nitrogen-containing organic compound containing ammonia to coexist in the reaction system. In the third invention, by adding an equimolar amount of an antimony halide to the nitrogen-containing organic compound, only the target antimony ethylene glyoxide can be reduced, and the purification process is unnecessary. Was able to do so.
6 6
差替 え 用紙 （規則 26) Replacement form (Rule 26)
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9/110312 | 1997-04-11 | ||
| JP9110312A JPH10287689A (en) | 1997-04-11 | 1997-04-11 | Method for producing antimony ethylene glyoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998046661A1 true WO1998046661A1 (en) | 1998-10-22 |
Family
ID=14532528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1997/003432 Ceased WO1998046661A1 (en) | 1997-04-11 | 1997-09-26 | Process for the preparation of antimony ethylene glycolate |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5910599A (en) |
| JP (1) | JPH10287689A (en) |
| WO (1) | WO1998046661A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004511814A (en) * | 2000-10-13 | 2004-04-15 | クラリアント・インターナシヨナル・リミテッド | Method for fractionating resin using static mixer and liquid-liquid centrifuge |
| US6512087B1 (en) | 2000-10-13 | 2003-01-28 | Clariant Finance (Bvi) Limited | Fractionation of resins using a static mixer and a liquid-liquid centrifuge |
| CN1891708B (en) * | 2005-07-05 | 2010-04-14 | 李绍通 | A kind of synthetic technique of organometallic antimonide |
| US8946486B2 (en) * | 2007-12-03 | 2015-02-03 | Tyco Fire & Security Gmbh | Method of forming alkoxylated fluoroalcohols |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS554130B2 (en) * | 1973-08-24 | 1980-01-29 | ||
| JPS5735840B2 (en) * | 1973-08-24 | 1982-07-31 | ||
| JPH09263588A (en) * | 1996-03-28 | 1997-10-07 | Tanaka Eng Kk | Production of antimony glycolate and antimony glycol oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3054760A (en) * | 1960-04-22 | 1962-09-18 | Hooker Chemical Corp | Polyurethane foam containing ethylene glycol antimonite or 1, 2-propylene glycol antimonite or mixtures thereof |
-
1997
- 1997-04-11 JP JP9110312A patent/JPH10287689A/en active Pending
- 1997-09-11 US US08/927,651 patent/US5910599A/en not_active Expired - Fee Related
- 1997-09-26 WO PCT/JP1997/003432 patent/WO1998046661A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS554130B2 (en) * | 1973-08-24 | 1980-01-29 | ||
| JPS5735840B2 (en) * | 1973-08-24 | 1982-07-31 | ||
| JPH09263588A (en) * | 1996-03-28 | 1997-10-07 | Tanaka Eng Kk | Production of antimony glycolate and antimony glycol oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10287689A (en) | 1998-10-27 |
| US5910599A (en) | 1999-06-08 |
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